Unimolecular decompositions of the radical cations of ethylene glycol and its monomethyl ether in the gas phase. Distonic ions versus ion-neutral complexes

Audier, H. E.; Milliet, A.; Leblanc, Danielle; Morton, Thomas Hellman

doi:10.1021/ja00032a014

Cited by 41 publications

(38 citation statements)

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“…40 In the present case, a carbon-bound hydrogen atom (e.g., D on C1) may migrate to a hydroxyl group to form an intermediate MOH 2 + (MOHD + ) molecular ion after ionization by charge exchange with an incident ion. 41,42 While in the gas phase it further proceeds with the loss of a CHO or water molecule, 41,42 on surfaces another channel may be open for the loss of an H 2 O + (HDO + ) ion. The latter then picks up the third hydrogen to appear as an H 3 O + (H 2 DO + ) ion.…”

Section: Fragmentation Mechanisms and Radiobiological Relevancementioning

confidence: 99%

10–100 eV Ar+ ion induced damage to d-ribose and 2-deoxy-d-ribose molecules in condensed phase

Bald

Deng

Illenberger

et al. 2006

Phys. Chem. Chem. Phys.

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We report that 10-100 eV Ar+ ion irradiation induces severe damage to the biologically relevant sugar molecules D-ribose and 2-deoxy-D-ribose in the condensed phase on a polycrystalline Pt substrate. Ar+ ions with kinetic energies down to 15 eV induce effective decomposition of both sugar molecules, leading to the desorption of abundant cation and anion fragments, including CH3+, C2H3+, C3H3+, H3O+, CHO+, CH3O+, C2H3O+, H-, O-, and OH-, etc. Use of isotopically labelled molecules (5- 13C D-ribose and 1-D D-ribose) reveals the site specificity for some of the fragment origins, and thus the nature of the chemical bond breaking. It is found that all of the chemical bonds in both molecules are vulnerable to ion impact at energies down to 15 eV, particularly both the endo- and exocyclic C-O bonds. In addition to molecular fragmentation, several chemical reactions are also observed. A small amount of O-/O fragments abstract hydrogen to form OH-. It is found that the formation of the H3O+ ion is related to the hydroxyl groups of the sugar molecules, and is associated with additional hydrogen loss from the parent or adjacent molecules via hydrogen abstraction or proton transfer. The formation of several other cation fragments also requires hydrogen abstraction from its parent or an adjacent molecule. These fragmentations and reactions are likely to occur in a real biomedium during ionizing radiation treatment of tumors and thus bear significant radiobiological relevance.

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Section: Fragmentation Mechanisms and Radiobiological Relevancementioning

confidence: 99%

10–100 eV Ar+ ion induced damage to d-ribose and 2-deoxy-d-ribose molecules in condensed phase

Bald

Deng

Illenberger

et al. 2006

Phys. Chem. Chem. Phys.

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“…Similar to fragmentation of protonated sulfonamides, dissociation of a2 affords an ion/neutral complex of [sulfonyl cation/imine] ( INC ) in the reaction channel of path‐1, with an energy barrier 228.3 kJ/mol via the transition state a2‐TS . INCs are considered important and interesting species occurring as intermediates during the fragmentation of gaseous ions . Direct decomposition of INC gives the ion 1PI at m / z 141, with an endoergicity of 63.2 kJ/mol.…”

Section: Resultsmentioning

confidence: 99%

“…INCs are considered important and interesting species occurring as intermediates during the fragmentation of gaseous ions. [30][31][32][33][34][35][36][37][38][39][40] To our surprise, a distinctively higher energy barrier needs to be overcome in the dissociation of the protonated sulfimides than that in the protonated sulfonamides (~100 kJ/mol). [14] In path-2, the formed sulfonyl cation, originating from breakage of the sulfimide N5-S6 bond, undergoes 1,5-migration to the ortho-site of the C-ring to afford an intermediate b, which surmounts an energy barrier of 123.8 kJ/mol (a1-TS2).…”

Section: Theoretical Calculationsmentioning

confidence: 90%

Dissociation of protonated N‐(3‐phenyl‐2H‐chromen‐2‐ylidene)‐ benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer

Wang

Cheng

Guo

et al. 2015

Rapid Comm Mass Spectrometry

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“…Numerous studies have therefore been carried out to elucidate ionization-induced isomerization/dissociation mechanisms. − Ethylene glycol (HOCH 2 CH 2 OH) is one of the fundamental ethane derivatives and is the prototype of diols. Neutral ethylene glycol energetically favors the gauche form, in which the intramolecular hydrogen bond is formed between the two OH groups. − It has been reported that the protonated methanol fragment is generated upon photoionization of ethylene glycol with the photon energy higher than 10.4 eV, which is near the vertical ionization energy. − Because a double proton transfer reaction is necessary to generate protonated methanol from ionized ethylene glycol, this ionization-induced isomerization/dissociation process has attracted much interest. (Here, we should note that the reaction is, strictly speaking, proton and hydrogen transfer.…”

Section: Introductionmentioning

confidence: 99%

IR Spectroscopic Investigation on Isomerization of Ionized Ethylene Glycol

et al. 2019

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It has been known that photoionization of ethylene glycol generates protonated methanol when the ionization energy is in the vicinity of the vertical ionization energy. Although two different isomerization paths have been proposed for the protonated methanol production, the isomerization path has not yet been identified. To investigate the isomerization of ionized ethylene glycol, infrared (IR) predissociation spectroscopy based on vacuum ultraviolet photoionization is carried out for neutral and cationic ethylene glycol and partially deuterated isotopomer (HOCD2CD2OH). The IR spectroscopic results indicate that ionized ethylene glycol isomerizes to the protonated methanol–HCO complex, and the isomerization path involving the double proton transfer is identified. This isomerization path is also supported by the theoretical isomerization path search, which demonstrates that several reaction pathways are mutually intercommunicated.

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Unimolecular decompositions of the radical cations of ethylene glycol and its monomethyl ether in the gas phase. Distonic ions versus ion-neutral complexes

Cited by 41 publications

References 0 publications

10–100 eV Ar+ ion induced damage to d-ribose and 2-deoxy-d-ribose molecules in condensed phase

10–100 eV Ar+ ion induced damage to d-ribose and 2-deoxy-d-ribose molecules in condensed phase

Dissociation of protonated N‐(3‐phenyl‐2H‐chromen‐2‐ylidene)‐ benzenesulfonamide in the gas phase: cyclization via sulfonyl cation transfer

IR Spectroscopic Investigation on Isomerization of Ionized Ethylene Glycol

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